Oil-in-water emulsion textile printing extender pastes



Patented May 5, 1953 osmosi LaISzlo-Auex:South Orange, N. J.

1 GENERAL:OUIIfINlL OFI' INVENTION s The"object o1?` ,thisinVentiUm is a nevvI textileprinting paste." This vpa'ste'is `particularly"suitV-n` able as .anextender of oilin`wateremulsionpig#A ment "color concentrates and as a 'carrier fof` "Vat. dyes in" vat dyestuii" printing.'

In present day, textile .printing withpigments' Wa;i'.e1'=in'-'oilV vemulsions "are usedM in the' trade;A in spite-of the fact, "that usolvent 'cleaning ofequip' ment' 4is "troublesome -in"te'xtileV plants; The"rea-1 son-for favoring Wyoftype emulsions isthat color" mileage' of pigmentsis greater"l in" Water-'in-oil' emulsions; `thanin voil-inevvater"emulsions:Y Pig-4`v` ments used for 'this purpose -are'hy'drophobie' and' tend to flush over'to the 'oilphaser Wherethe'nil` phaseiis continuous; like in Wf/o; emulsionsfit 'is easyto keep "pigments completely defloeculatedz" and they 'yield'fhi'gher "'color Values. Iniloilin- Water emulsions; if pigments are incorporated into -Water phase," Waterl is l"the continuous phaseI andracts` `as '..b'arrier against' tiiushing- Y and" consequently :lower I color `values v'are "obtained, Ifp'ig'#r ments fare'incorporated"into";the "oil 'phase'ofan oiii'nlwater emulsion',`- emulsiiication` is'fmore' difc'ultj' degree` of dispersion is *of reduced ""char'" acter'andoolorva'lue stays low.

For-'printingjpurp'oses pigments""are"usual1y1int corporated into so calledtcolo'r v:'concentrates,

mented"emulsionst= Solventcontaining"oiywrexwL tender'-print Epastesfoithepriori-arteontain largev amount "'of solvents. f' andi improper 1proportions tor selection-of protective 'collidsf Tl'ustheydi'dnov yield-proper"colorfvalueg ifefpigmentfmileage.

In vat dye printing the vat'dyestufisfarefap pliedasf pigmentsgiare #converted-vfonithefabric' to Waterffsoluble leuco f compounds'fbyereductionf and1t are ^`re=oXidi2ed "on the-fabric; depositing "minutei pigmentpartio'les'in-thelbers Conventionalvat" printingisfcarriedfout with:'starchipasten-British*- I'df'l'gOSUlSrOtiacididys Dri-fabrica andfrepresent"v fthatprints' may be storezzlfsafelyA beforeagin'gandJ even roller printers nd it of great convenience ii Aprinting .has not to be strictly correlated with ager capacity 'and :prints"'oan"be stored-before aging;v To' satis'iy"thi`sdemand"the"socalledy C1lrsin'e"type printing Was developed,l which is also known "as"Ce`l1apret 2 method in this country' The essencefof" this' method isV the in# eo'rporationof methyiicellulose as-'temporary pige the "Vat pigments" 'are' dispersed first in a starch" past'e and incorporated'ias `suon into 'the "methyl cellulose paste.7 'Ilie`v print paste does not l=containreducing. agenti and can' bestored -for `consider-"- able tinte;y f A stronglyE4 alkaline f sodiumffhydro1'V sulfite solution is padded on the printed-"fabricI before aging;r or a milder-alkalinesulfoxylate'padding may fber. applied. Padding'is carried'out' hot;l so 'thatthem'ethyl"oellulose'remains 'undissolvedy being insoluble in hot Water and in'strong"alkali,y

and therefore protects'the" print from bleeding out Ofi` lines?, .t Thezipaddedfiabric' .is `agedraridi reoxidizeda.L The washingioutt of the methyl ,cellulose andestarchais 4asrreat probl'emin'thi's' type offprint-a` ling, as methyl cellulose requireszfeold:rwateiqand? starch hot Water for removal. Both have to be removed to obtain softihand `of the print. The print. 'apastesfioi athis@ invention#v permit torobtain go'odf;':rcolor:;1f.yiel`d; permit .storage :of: printsrffori longerfperio' ds Without damage;4 beforexaginggi and. dotnet :represent :or i presenti-problems.` in removalN of.-..gumsfraftrzaging intheisoaping operation particularly useful if pastes are applied to pigment printing. Further optional ingredients are: (5) surface active agents in minor proportions, and (6) sulfoxylate. The latter is used if discharge printing is the aim with pigments, or if vats are printed and discharge or reducing agent in print paste is required.

NATURE AND PROPORTIONS OF INGREDI- ENTS Cellulose ether The cellulose ether is either` methyl cellulose 0r carboxymethyl cellulose, applied as water soluble salt. The preferred methyl cellulose grade is the 4000 cps. type, but Viscosity may be lowered to 1500 cps. type grade or any grade inbetween these two limits. In case of water soluble salt of carboxymethyl cellulose, sodium, ammonium or triethanolamine salts may be used. I prefer the sodium salt and use the highest obtainable viscosity grade. Commercial definition of sodium carboxymethyl cellulose is different from that of methyl cellulose, but the high viscosity sodium carboxymethyl cellulose yields just slightly lower viscosity solutions in water, at equal concentrations, than the 4000 cps. type methyl cellulose.

By weight percent, the print pastes of this invention contain 0.3% to 0.8% high viscosity cellulose ether. Based cn 100 parts of Water in the print paste, the cellulose ether is from about 0.7 part to 1.6 parts.

For pigment printing purposes I prefer methyl cellulose as the cellulose ether, as it yields greater brilliance of color and somewhat increased color mileage. In case of vat dye printing, most vat dyestuff pigments show greater color yield with sodium carboxymethyl cellulose, whereas a few show better yield with methyl cellulose. For discharge printing, where sodium formaldehyde sulfoxylate or the corresponding zinc salt are present in the paste, sodium carboxymethyl cellulose shows great advantage over methyl cellulose, as carboxymethyl cellulose salts have higher electrolyte tolerance apparently and do not cause pigment flocculation upon addition of electrolytes.

In case of other dyestuffs, both types of cellulose ether are suitable, but one may show advantage over the other in color yield with one,

individual dye.

Water The water content of the print pastes of this invention may range from about 47 to 61 1/2 but preferred top limit is 55%. Higher water content reduces color value.

Solvent The solvents of this print paste are water-immiscible. Most favored solvents are aliphatic petroleum solvents, such as Varnish Makers and Painters naphtha, various grades of mineral spirits with Kauri Butanol values from 33 to 46 and flash points of 41 to 150 F. Flash point of 100 F. minimum is of advantage, on account of lire hazard. Aromatic solvents may be used,

4 like toluol, xylol, I-Ii-Flash naphtha (high flash point solvent naphtha) and mixtures of aromatic and aliphatic hydrocarbons yielding varying Kauri Butanol values.

Water-immiscible esters, ketones, ethers and alcohols may be present to obtain special effects, but their use in larger proportions may increase raw material cost greatly.

Generally speaking, solvents, which evaporate ahead of water from the print paste, will yield clear and brilliant prints right away, whereas slower evaporating solvents, which remain after main portion of water evaporated, will cause a temporary gum blush, from cellulose ether deposit on top of print, which, however, disappears if print is exposed to steaming or Soaping. On account of flash point and nre hazard considerations slower evaporating solvents are preferred, but where prints are not exposed to steam or water and are sold after printing, it may be necessary to use faster evaporating solvents, to avoid gum blush effects. Varnish Makers and Painters naphtha (VM&P naphtha) and xylol are examples of the solvents, which leave water at the end during co-evaporation. Mineral spirits fractions and Hi-Flash naphtha fractions will permit e. g. water to evaporate ahead and they stay in major proportion of volatile part towards the end of evaporation.

With regard to brilliance, aliphatic hydrocarbons yield greater brilliance, than aromatic hydrocarbons.

The solvent content of the print pastes of this invention may range from Ll31/2% to 51%% by weight, and are in volume percents generally larger than 50% of the composition. The weight percentage may go as low as 38% of the composition in exceptional cases, but such lower solvent content causes generally speaking lower color values and lower degree of brilliance.

Based on 100 parts of water by weight in the composition, the solvent parts are to 110 parts by weight, but in the exceptional cases, mentioned above, may drop as low as 621/2 parts, with the noticeable loss in color value and brilliance.

The specific gravity of solvents used varies greatly. VM&P naphtha has one of the lowest, specific gravities and Hi-Flash naphtha has one.

of the highest specific gravities. In emulsions the volumetric proportions of dispersed phase to dispersion medium counts and in the print pastes of this invention the volume of the dispersed solvent phase always slightly exceeds the volume of the dispersion medium: water. However, the volume of the solvent is never as high as double that of the water volume.

Extenders, for oil-in-water pigment printing- 91,009, filed May 2, 1949, to which the instant' application is a continuation-in-part. The

gum"solutioninwater type extender pastesA have the further disadvantage, that the gums stiffen the print and have to be removed to ob-A tain soft hand. Such removal may take part of the pigment with it.

In water-in-oil type pigment color printing, water is used as bodying agent of the extender print pastes. The art tried to use solventsfor bodying effects in extender print pastes, but very large quantities of solvents were necessary to obtaiirthe:I requiredAv printingT consistency; suclras Zf-tot 450`partsof solventfb'y Weighttto 1001 parts of-"water ibyweight: -I found, thatsexcessiveisol'- vent content in'h extenderr print-pastes, lowersy colorf mileage' and l colorrbrilliance-fof prints with oilin'water resinf emulsionV pigment" color' concen-trates;`

I'fiiave also '.found,l that theiproportonslof the ingredients# of the printrpasteslo-f thisy invention are very-critical to Yobtain high color= value;- and color brilliancefwith pigment: color concentrates;- Increasing water contentl. orf' increasing@ solvent content with corresponding-necessary adjustment in" proportion off thee cellulose-ether; all? lower color value-f and brilliance:y Evenlowering viscosity offthetype Of'fcellulose ether used;- orilowering its quantity below-4 tiie minimum limits given; will=lower color-"valueand briliiance.-

Thervariationsin color value-are of-great magnitudes If` incorporate e.l gf one@ pound" of ph-tlialocyanine blue1 into one gallon color i' con centrate and prepare in one case=anfoilinwater emulsion. and in the.; other. caseya. waterfin-foil emulsionand establish, usingtheflatter (vm/0.) color concentrate; anda..v conventional, extender pastev ofthe w./o. type: a shade of 1:20 extension cut (1 colorconc: and' 20* extender); to matclitthecolorintensity with ther-formerly men tioned 0./W; color` concentrate and using conventional extender pastes; We `have tol go ashigh. as..1:5: or; 1.':10`eXtensioncut: This means', in other words,` that'- thel color mileage of w-./o. emulsions is'twice to ourtimes as high as-tliat of'an oil-in-water-emulsion, orthat when using 0./w.` emulsionsl wev have toincrease pigment contentI to" double or4 quadruple to get color intenstysimilar to'a w.'/0'. emulsion with single unit pigmentation: In--a'dditiOn--the brilliance of conventional 0;/W.I prints' are lower:I than brilliance of"w./o-., emulsions. The" extender print pastes of this invention; would match ther above 1:20 extension cut with 1:21' orx1124loutand yield increased." brilliance and notf reduced brilliance; when compared 'with' thev comparative wu/o. emulsion color. print; Therefore; ittcouldzbestated, that when increased color-yield orfincreased 4brilliance.zv is. claimed as the: result off the extender printpastes usedinthis invention, the magnitudeof difference is in then range` of`50"to-400% and' not of," just afew'` percents, hardly, measur-l able-.or visible..

Further, in printing vats with thev novel eX-, tender-print paste, yieldssharp` lines, permits storageof prints for longer periods, preserves lineslfr'om bleeding during Vpadding with hydrosulntesolution andgdoes, not represent problem of removal by laundering, `as prints are softand lofty as printed and' Withoutlaundering. The latter property makes these pastes.v ideal for use with protein .bers, like f wool and silk, where scouring, with Aalkaline soap solutionsl shouldA be avoided asmuch as possible.

Concentrated resin emulsions in'vidrierasA `re-in forcing agents AdditionA of concentrated resin: emulsions f to the extender print pastes of`tlriis`invention; is particularly of advantage, whenJ tlie'- pastes-are usedfor pigment printing. Solventsandwater evaporate. Methyl cellulosev or carboxymethyl cellulose remainon thefiber; Both are' soluble in water; the former-more in Coldwater. They have to be insolubilized, to'preservefull-intensity of Y print, as` obtainedi The binder emulsion :pore tion"A of4` the pigmentA colorf concentrate,l may.

novel and unexpected discovery.l

achieve such ,insolubilization:inisliortextensionsi where: comparatively i larger: proportions; of color, concentrates. aref used; but: longer: extensions ythis wouldl not' work.- Therefore incorpora-ting;

resin emulsions into the extender print pastesiis of advantage.

For this', purpose.' It maya use from@ 1/4%.=; u-pto 31/21%' ofresin emulsion, .alsocalledihereinlasxexe tenderconcentratef resin?. emulsionI c in?.y theft, total print. pasteextender.. If such resin emulsion is present, the limits ofproportionsfof 'thebase ingredients relates to the portion free of resin emulsion: EL g. ifl'Ii'use 3%xof resin `=ern-Lilsiolrextender concentrate-inthe extender andl9z7 %=1 of thef abovel described 3ingredient extender'zfprint.

pasta; the'.` interrelationslfiip.` of" the: Siingredients relates to the 97% .portion,1 taking,same:as z100%'..

Extender resin emulsion` concentrates arable-.-

scribeddn my co-pending, application. Ser. No.

91 ;069 abovereferred Y tof and -will` be described Surface active agents,`

Itsl'lonldlb'ey pointed out, tha-tthe extendenprint pastos of this I emulsion are vcharacterised. tbv-larok of v emulsifying agents,` asv the cellulose-ethers take the place oi 'both emulsifying-sagent andjprotecetive colloid or stabilizer. 11i-many instances, particularly where lower solvent content is desired, or where Vcolor Vvalue should be iurther increased, or better penetration-is-requiredg the additionmf surface active agents is useful; Whereas-larger quantities are permissible,I'use'from 011%2to -1% of active surface active" agent perl6@ parts=cf print paste. Sodium lauryl alcohol suliateffis` one example oi such agentsand it tendstOimprUVe Washability with methyl cellulose containing' print pastes, whichV is` contrary to `expectationand is' vla Antifoam agents'may also ybe incorporated and some willfbe listed in the examples.A

Sulfoxylute;

Form aldehyd-e lsulfoxylates4 may beincorporated into print pastes-ofthis invention;v to producedisf charge printing past@ estendere; Sodiun'rY carboxymethylcellulose'v isr a` satisactory `ingredient in such pastos.

Trade names ofresz'ns suite-bled@ -Teeinforcifzgry resin emulsions;

Epichlorhydrin and bis-phenol" condensation 'product (alcohol) Epon 100e, .dehydratedcastor oil fatty ester of Epon 1G64: EpiteX 129.

Styrenated alkyd: Styresoll 4250;

Phthalic anhydride-free styrenated'alkyd: Soya fatty acid ester of carbo'anhydride `(bicycle 2"-21-1 cycloheptane delta 5 dicarboxyliclanhydridel) and`glycerine(coester off-fatty acids andV anhy- Viscosity grades of methyl cellulose and carboxymethylcellulose According to the Dow Chemical Company, Midland, Mich. (The new Methocel, Powdered Dow Methylcellulose, 1949 edition) in 2% aqueous solutions the absolute viscosity of methylcellulcse grades has the following limits:

Viscosity type and average Viscosity Viscosity determination method as described in here referred to Dow bulletin. From point of view of this invention l cps., 15 cps. and 25 cps. grades are considered low viscosity type; 100 and 400 cps. grades are considered medium viscosity type and 1500 and 4000 cps. grades are considered high viscosity type.

According tov Hercules Powder Company, low viscosity sodium carboxymethylcellulose has a viscosity of 25 to 50 cps. in 2% aqueous solution; medium viscosity sodium carboxymethylcellulose has a viscosity of 400 to 600 cps. in 2% aqueous solution and high viscosity sodium carboxymethylcellulose has a viscosity of approximately 1500 cps. in a 1% aqueous solution. Note, that H. V. type is measured in 1 solution.

Antifoam agents Methylcellulose is a strong foamer and CMC foams too. Antifoam agents may be used in quantities ranging from 0.005% t0 0.100%, based on extender print paste. For methylcellulose containing extender print pastes most effective agents are, according to this invention, silicone compounds, like DC Antifoam A emulsion, Span 20 (sorbitan monolaurate), Span 85 (sorbitan trioleate), and Emulphor AG (described in examples), alone or preferably in admixture with each other. In a surprising manner it was found, that ammonium thiocyanate, in quantities of 1/2 to 2%, based on methylcellulose content, eliminates almost completely the foaming tendency and yields long, string print pastes.

The following examples illustrate the invention. All percents and parts are by weight, except where volume parts or percents are specified.

EXAMPLES Example 1,-Concentrated oil-in-water resin emulsion, suitable to reinforce pigment printing extender print pastes.

42.15 parts of E-polyester resin of Example 2 of my co-pending application Ser. No. 91,009, above referred to (dehydrated castor oil fatty acid ester of an alcohol obtained by condensing bis-phenol and epichlorohydrin), dissolved in xylol and having 50% non-volatile (N. V.) content, 0.31 part of mixed naphthenate driers,

12.22 parts of 10% sodium lauryl sulfate solution in water, 20.65 parts of a casein solution in water containing ammonia, said casein solution containing antifouling agents, 5.48 parts of ammonium hydroxide solution prepared by mixing 1 part of concentrated ammonium hydroxide and 1 part of water, 10.54 parts of 20% water solution of sodium carboxymethyl cellulose, low viscosity type, and 8.65 parts of Water: are made into an emulsion in the following manner: Add to the resin solution 2A, of the sodium lauryl sulfate solution, mix the remaining 1A; with the water and the casein solution in a separate container and add then to the resin solution containing mixture `under agitation, this latter mixture of emulsifying agent, casein and water, slowly, in increments. Add the ammonium hydroxide solution v and add finally the sodium carboxymethyl cellulose solution. Homogenize the emulsion obtained. This emulsion is suitable as additive to extender print paste emulsions of this invention, to re-inforce same.

Example 2.-Emulsion-polymerized oil-in-water resin emulsion, suitable to re-inforce pigment printing extender print pastes.

An emulsion-aggregated (polymerized) binder is prepared from the E-polyester solution used in Example 1, according to Example 1, by the following changes: deducting 3.58 parts of the water added and replacing it with 3.58 parts of a 30 volume percent hydrogen peroxide solution. This kis added at the stage after which ammonium Example 3.-Melamine-formaldehyde resin containing oil-in-water resin emulsion, to reinforce pigment printing extender print pastes.

The emulsion of Example 2 is repeated with the following changes:(a) 10% of the E-polyester resin solution is replaced with a 50% solution of a butylated melamine formaldehyde resin, having 50% N. V. and 20% xylol and 30% butyl alcohol as solvent. A suitable resin is Melmac 245-8. (b) The sodium carboxymethyl cellulose solution is replaced with a water solution of 20 parts of low viscosity methyl cellulose, 15 cps. type, in parts of water. The resulting emulsion is suitable for the same use as the products of Examples 1 and 2.

If methyl cellulose, low viscosity type is used, this may be present during the stage of emulsionaggregation, i. e. when the hydrogen peroxide is incorporated.

The E-polyester resin of Examples 1 to 3 may be replaced with other resins mentioned further above, such as styrenated alkyds, styrenated oils, etc. The melamine resin of Example 3 may be replaced with other amine aldehyde resins, such as urea-formaldehyde resins, substituted (alkylated) urea-formaldehyde resins, substituted (alkylated) melamine-formaldehyde resins, similar amine resins formed with other suitable aldehydes, etc. 'I'he organic solvent soluble aminealdehyde resins are usually ethers of low molecular alcohols, such as methyl, ethyl, butyl, capryl i9 dalcohoL :To lai/'oid "-water-solubility, :which may l'disturb wemulsions, chain .length .from v:butyl to capryl are preferred.

15.90 ,parts of the emulsionof Example 3, .147 .05 parts-of` a 3 4Water solution of 40Go-cps. methyl cellulose, r47.05 .parts of yWater .are mixedend homogenized. Under l agitation zwi-th a suitable mixer, like theEppenbachfI-Iomomixer, lOOffparts vof .mineral spirits lare stirred into the lforrner `emulsion in increments. The mineral Aspirits `used in this example -has fa bulking Value of v0.1515 @gallon per pound, l a ash vpoint/ol? 100.-- .aJK-auri-Butanol value-of 44 to 46,and.is-marketed under `the vtrade name .of -Amsco-ll/Ilneral .Spirits-#46.

Example s-.Re-inforceid extender :print .tipaste lWithxylol.

Example 4 is repeated,v replacing the mineral lfs'pirits' With xylol, havlnig'fiaf ash f'point of tabou-t 81 "and zaf'fbulking walue "ef 0.1385 v-igallorrlper pound. The viscositydofitnis 'emulsion islsomewhat .lower .than that of :Example .4.. as the volvurne 'ofthesolvent is :less in thisexample, than .inllllxamplea Whereasthe YWater.phase volumeris f thel same.

Emample Ll Water diluted v extender l-print; paste with xylol.

scoparts df 'extender;printpasteiff"Example fare fdilutedvithll() parts of Water. AAsinl'ar cliluted emulsion may be' made 'from Example '4. "This "diluted "type of extender yields flower col-or lValue' and lower' brilliance'fwithoillinlwater'resin le'mulsion color v'concentrates,",thanithe :emulsions 'f "Example 4 or 5"respectively, lhoweverjlio'r some purposes like in screen printing, Wherehigh --penetration isrequired, theyfgmaymeuseful.

Example 7.-Re-inforced extender print .paste with .mineral spirits, volumetrically .similar to Xyll extender` of,'Example 5.

. solventftof'water phase "is 1 similar "tothat" of :the extern-deref?creampie s-exyion ,leases-'pareca Y23%?InethylcelluloseSolution'in'Watettzusing4000 'cps rmethylcllulose, 23.563' partsy of A"-ylf'ater 'Iand "2E8'74Jparts reif concentratedj'resin emulsonw'of Example*Spare mixe'dandel parts of mineral "spirits Ao Exam-ple 4 I"are incorporated, "'as fdc- Cscribed inExample *The resul'tirg emulsion V`iiatstalfverysirriilarfvisccsity"to that nfthejproduct ,y --of Example 5. :""This extender emulsion hasahot 120 .739 "methylcellu-lose, 4'8-9'9% Water, 47175973 jofsauvent"and.003%f re-inforcing concentrated .resin emulsion.

"ExrENDEa-.Pmur Pnsmns 'sWIrHoUmRn-INFORCING, RESIN EMULsioN .Example FSF-Viscous *emulsion *with :.I'nineral spirits.

017.50 V4part i. of oscps. high viscosity .methylcellulcse -is dissolvedfin 49.250.1'parts-of Water. 150 .parts .of mineral spirits of Example- 4 .is incorporatedin increments, under proper agitation. A Visco-us; print fpaste ,is obtained.

Example is: repeated; using 1500 cpsfmethyh cellulose;k instead 4ofthe i000 cps. type used'in Example 8. The resulting emulsion hasfamoldilc printingconsistency. It yields a trace lower color 'value,` thanY the'rprodut of- Example 8` with oil-in- `Water resin emulsion colorconcentrates, but-may have advantages, Where higher penetrationislelouired? kor lower Viscosityis needed for some pur- Apose. -Shallow engravings or screen `printing are examples Where .itmayl beused.

1'9'0 n'parts r"of the emulsionf Example 8 "are "mixedwitn101partsf a"'10'% solution of sodium `..lauryl'sulfate (DuponolME) inwaten Normally dilutingfthe extender print'paste of thisinventionmwith Water, lowers the colorva'lue. "Incorj'por'ationof" surface active l'agents "may 'counter- "act" such lowering of `vcolor"value. `Sodium' laur'yl sulfate is given 'here'as an example of afsuitabl'e '25 agent. "This 'agent increases the 'viscosityfof 'methylcellulo'sesolutions if "added 'in `smaller proportions In the present instance,- in spite of' the `Duponol, the' Viscosityincreasing `action "of Dupo- 0 crME on' methyiceulfnse, increases the viscosity of the Water phase and'therebya"=heavier"paste is-.obtained .than before the Duponol ME solu- .tio-n was added. This .viscosity increasingaction also reduces the re-solubl'ilizing tendency of 235 methyiceuuioss and yields prints with increased laundering resistance.

Example 10 is repeated,"us`irig5%s'lutionof .sodium lauryl sulfate, instead of the 10% solution used 'in"Exarnple"'10. y`l'.esultirig' product' is fslightlyrless viscous.

spirits of Example 7 type Without relinforcing emulsion :.An extend'enprin-t was prepared Ito have similar 59 'Scomponent constitution *than in Example l'7,

Without the :use 'of Tre-informing concentrated methyllicellulose'fiveredissolved invlfi'! parts of wwater#and under fslow incorporation Ain incre-- `.55 `ments*=l7 7:59r .parts yoffsmineral: spirits was-added,

@under agitation fof fan Eppenbach Homomixer.

This mixeris ahighspeedfturbomixer,Where:the "turbine"rotatesineaistatorlring housing-Withuna 'ro @clearance sand 1' the' -rnix'er' rotates Withfabout @0f-35005K M. FThe :mixer-is suppliedWith-an adjustablefballei plate: and vthe mixer itself "can be lowered or raised in the container in which the uct of Example 7. In this emulsion `ony `ljg arts ofy a l1/2% methyl cellulose solution in Water:

@5517 1- parts of mineral spiritswereused.

Eample "l- Extender .print paste emulsion,

.similar to Examples hut/With .methyl-y cellulose lfcontent lowered tol half.

'OLBFZpart ofOOO cps. methyl Ycellulosa'high viscosity type, `wasfdissolved in 49.625 parts of walten. yielding a Waterapliase with0.75% -methyl cellulose content. -'50 parts vof -mineralspirits used in Example 4, were incorporated into the water phase under agitation, the solvent being added in increments. The resulting extender print paste has a viscous, flowing consistency and can be used where lower viscosity pastes are of advantage. v

Water soluble amine-formaldehyde resins or amine-aldehyde resins may be incorporated into the extenders of this invention and they faciltate the insolubilization of cellulose ethers, by curing them on the action of heat. Trimethylol melamine and hexamethyl melamine may be used, or their water soluble alcohol ethers, such as methyl ether or ethyl ether. Aerotex M-3 resin is a methyl ether (trimethyl ether) of trimethylol melamine and is marketed in a water Solution with 80% non-volatile content. In this example 99 parts of the extender print paste of Example 11 are mixed with l part of Aerotex M-3 resin. The resulting extender print paste vyields prints, which when cured properly, will yield extremely laundering resistant prints. Catalysts may be added to the emulsion to catalyze the melamine resins curing. Diammonium acid phosphate, ammonium sulfate and benzoic acid may be mentioned as suitable catalysts.

Example 15,-Extender print paste with 3% water soluble melamine-formaldehyde resin addition.

97 parts of the extender print paste of Example 11 were mixed with 3 parts of Aerotex M-3 resin solution. A similar extender print pastels obtained, to that of Example 14, but with increased melamine resin content.

VARIA'rioNs oN RE-INFoRcED Ex'rENDER PRINT PAsTEs Example 16.-Extender print paste of Example 4, where one half of methyl cellulose is replaced by water.

0.353 part of 4000 cps. high viscosity methyl cellulose is dissolved in 46.773 parts of water. yielding an 0.75 methyl cellulose solution. This is mixed with a cencentrated oil-in-water resin emulsion of Example 3, taking 2.874 parts of the latter. The resulting product is agitated and 50 parts of mineral spirits of Example 4 are incorporated in increments under proper agitation. The resulting print paste is similar to that of Example 4, except, that on account of 50% lower content in high viscosity methyl cellulose, its water phase and consequently the emulsion has lower viscosity. The product is a fluid viscous emulsion with good printing qualities.

Example 17.-Extender print paste of Example 4, where one quarter of methyl cellulose is replaced by water.

0.530 part of 4000 cps. methyl cellulose, high viscosity, is dissolved in 46.596 parts of water. 2.874 parts of the emulsion of Example 3 are added and well homogenized with the methyl cellulose solution. 50 parts of mineral spirits are then incorporated in increments and under proper agitation. The resulting print paste has a consistency (viscosity) higher than that of Example 16, but lower than that of Example 4. The product has good printing qualities.

1'2 Example 18.--Extende1- print paste with reduced proportion of re-inforcing resin emulsion content.

In the products of the instant invention the addition of re-inforcing concentrated oil-in- Water resin emulsions increases cost substantially. The resin emulsions are added to improve crocking and laundering properties of pigment prints. In many instances the proportion of resin emulsion can be greatly reduced and performance still maintained. In this example the product of Example 4 is reproduced with 50% lower resin emulsion content. 0.707 part of 4000 cps. methyl cellulose is dissolved in 47.856 parts of water. This solution is mixed with 1.437 parts of the emulsion of Example 3; and 50 parts of mineral spirits of Example 4 are incorporated in increments into the mixture, under proper agitation. The methyl cellulose solution of this example can be made by taking 23.563 parts of a 3% methyl cellulose solution, high viscosity, and adding 25.000 parts of water. The resulting product has viscous pasty consistency.

Example 19.-Extender print paste with reduced proportions of re-iniorcing resin emulsion and methyl cellulose contents.

In this example a similar product is made to that of Example 4, but the resin emulsion content and the methyl cellulose content, both, were reduced to 50% of the original. 11.782 parts of a 35% solution of 4000 cps. high viscosity methyl cellulose in water was mixed with 36.781 parts of water. This mixture contained 0.353 part of methyl cellulose and 43.210 parts of water. This mixture was mixed with 1.437 parts of resin emulsion of Example 3 and homogenized. Under proper agitation 50 parts of mineral spirits were incorporated in increments. The resulting extender print paste had mobile flow and could be used with advantage where lower viscosity print pastes are required.

Example 20.--Extender print paste with solvent volume half way between that of Examples 4 and 7.

This example shows regulation of viscosity by the aid of solvent proportion, still remaining in the range where high color yield is obtainable. The solvent volume in this example is half way between that of Example 4 and Example 7. 0.722 part of 4000 cps. methyl cellulose, high viscosity, was dissolved in 47.437 parts of Water, mixed with 2.937 parts of resin emulsion of Example 3, homogenized and after proper homogenization 48.904 parts of mineral spirits were incorporated in increments, under proper agitation. This formulation could be written in a manner, that to 50 parts of the Water phase of Example 4, containing the resin emulsion of Example 3, 47.855 parts of Amsco Mineral Spirits #46 was added. .The resulting product is a medium viscous extender print paste.

Example 21.Extender print paste with V. M. & P. naphtha and solvent volume similar to that of Example 7.

To 54.55 parts of water phase of Example 4, containing the resin emulsion of Example 3, 45.45 parts of V. M. & P. naphtha was added, having a ash point'of 41 E., and bulking 0.1645 gallon-per pound (6.08 lbs. per gallon). The product of this example had 0.771 part of methyl cellulose, 4300 cps. high viscosity, 50.643 parts of water, 3.136 parts of resin emulsion of Example i460() wps. ametllyicellli-lose.

#Btanii'fsflleiparts "f V.:M.f;&1P.maplitha. 'lfrlie `meisultingffemmxlsionhas similar .iscosity .thanthat .fo'fFExa'mpleW fleeing. mobilefflnwingiwstemnd A:is :particularlyrsuitable yfor screen L printing @with pigment containing 'xoj/ sin yermilsion color cencentrates,fwlxere'ethe ntsfsarenetsscneduled 4tobersoapedaorfsteamed before anark'eting. .The .'fM. it; iP. inaplitha cevaporates iahead Y"of -Sit/atei* vand #therefore ith-s ipa-ste e:does :not .iv-yield :methyl ,oelrlulose gum fblush .son @top fof gprint. .zelt ,f1-yields :original maximum :calor wallie with great ,fibril- :lian'ce ,LEor sake of flaiity, Tit shold :be intentioned 2thatlthesolventwolume, disregarding'fsoivent con-- .tentlaof :reeiniorcinig 4resin mulsion, .in Example 1 44 fris "i5 .73%, .Examples V5 lfand l7 :53 .51% .,f .the total .volume-fo`ff.the;iprint paste. -In `Example ipusing .'fxylol, the solvent evolume :is 40 :81 :fand elsing @mineral :fspirits in the y:.-sarx-re `example fthe :solvent'ffvolume vis 422993611 ume units of Water phase, containing @the resin emulsion, :the #solvent .volume :is :sin Example 4; 1.25.9andrinaExanlplei; 1l5lf1 volumeiunits IExTnNnEsiBnmmihrsTmsWITHQCARBOXY- METHYL-Cmmosn :Example .22.--'IXyl'l "extender fprint paste "with "CMC sodium -scarboxymetny-leellulcse instead fof :the The znleh fvisccsity type:carnoxymethylcelllose,rtokbecealle urtirer fbelow f' `as N.,:;tsnows .approximately `2000 cps bythelHerculesffall i gb'afll: mettrodfandzs manintactured?abyltheercles,.Bewderlcclnpany.

vlulose ofExample.

..Emampla??4.-lMineralespiritszextender-:pritpaste i l I, 'Examples 33, 34, "3'5 'and "'3'6.-Examples "with .Example 44 is repeated, freplacng tCMC LH. t

.for `methyl cellulose Example "zrffilxower solvent `volume' itype '-'ninferalspirts#extender print paste with CMC.

Example `'l is repeated, replacing iH. N.

for methyl cellulose.

...Example .2dr-Lower solvent "volume :type .1min- -feralzsp`irits.wtendergprintlpaste:with CMC,not iusingre-,inercing resinemulson.

nxampleiz its repeated, replacing GMC LH. ifcrmetnyl'cllulose.

#Example Tr-Lower 'solvert volume itype mimferal'spirts :extender print peste wltnfGMCend Esskllre inforcirlglemilsien.

Example H is .frepeated replacing CMC AH. .fer lmethyleeelluloee and vusing a reinforcing emulsion similar to the one used iniExample, J1, but replacing the dehydrated castor oil ester resin methylcllloseendbupendliME sllition.

Smparts of extenderfprint,pastevwasr mixed Ywith 10 partsnofduponoliL/LE 1solution Iin water. Example 33, usiner print paste of Example and a 3%"Dupono'1`f-ME sliition. Eixample B2i, 'using *print paste fof Example 6 .zxylol -andfa 3% @upenolMELsolution Example d, fusing 1p1-@int .paste ..df Example 32 fxylolf) i andra :Dupcnol ME solution. Example36 using print vl.pasteof Exampletllvlsp.

aand?a22,% iDupeI-lol MEssolution.

iIn'tlrefaboveXamplest-'nofsemulsifyingriagentiis present, except where '.re-einforcing iiresin eemlfsiensrareused. .rlntheil'atterfcaseitheirfemulsifywing 'agent is ,presentin the .printgpaste .Addition v'et-eznulsifayingagents imayzbe desirable .for-variyoils rrleasonfs. iSomezrare listed s'here': ifurther iiniereasecfstability; easier.:mixing'with'fdycsnepiement dispersione and pigmentzenlonjconcentrates; reduction `of .foaming tendency; `avoiding `gum "ilush With'e.f'grmthl'celliilose -Gum blush, asfawlii'tefslig'litly opaque deposit iditraeesinflmthylcellulese,@camberobservedge. g. en pigment rpifrnts, militare lasolvents evaporate xsliewer i than mater, .-lilze @the @mineral spirits used in some of the examples. zl/TJM.&rR.naphthatan Xylol do notshow suchgum blush. The gum fblush disappears upen soapng y"er isteaming, vlout emanyltimesiprints are marketed wthouttettertreatment In following examples `:to 21100 parts of ex- E'tender @pil-'int paste sof Example 4, .11 part o'f :sur-

face 'active regent was added. l'llhe eXamDIesJiS't Miesurfaceactive agentsused.

.with allmseedroil, which wasimcdiedwitn maler@ 27o Example 3a-42% "Emlphor lG, ethylene foxiiie anhydride (about 5%?) `land zetter :condensation its #acidity was rester-ined with ipentaerythritel. Such an oil is marketed undertheitrade name of Esskel. {Ehei'oilris'fleodieditoraz-vvlscosityhbefore Ldilutinglitiwith mylol, to 5.0 JN.

Example 41 .'-Aerosol OT, dioctyl sodium sulfosuccinate. Anionic. 1%.

Example 42.-Sterox SK, polyoxyethylene thioether, nonionic. 1%.

Example 43.-Avcolube 100, sorbitan mono palmitate 50% and polyoxyethylene sorbitan monopalmitate 50%, mixture, non-ionic. 1%.

Example 44.-Atlas G-2859, polyoxyethylene sorbitol 4,5-oleate, non-ionic. 1%.

Example 45.-Victawet l2, phosphoric acid ester, in which one of the hydrogens of phosphoric acid is replaced with a medium chain alkyl group (like polyethylene glycol radical) and two of the hydrogens is replaced with water solubilizing groups of alcohols of medium chain length. 1%. Non-ionic.

Example 46.-Victamul 89, non-ionic organic ester of phosphoric acid. 1%.

Viscosity of the surface active agent containing print pastes ranged in the` following order, from most Viscous to least viscous Victawet 12, Tergitol 7, Atlas G-2859, Emulphor AG, Avcolube 100, Victamul 89, Ethofat 142-20, Tween 85, Aerosol OT, Sterox SK. With regard to avoiding gum blush in pigment prints, best results were obtained with Emulphor AG and Atlas G-2859. Victawet 12 gave very lively colors. Emulphor AG reduced forming tendency of paste most effectively.

Ex'rENDrB PRINT PAsTEs WITH CATIoNIc RE-INFORCING RESIN EMULsIoNs For many purposes cationic emulsions show advantages. The extender print pastes of this invention may be made cationic, either by adding cationic surface active agents to the non-reinforced print pastes, or using a cationic re-inforcingemulsion of resin as re-inforcing resin emulsion. Example 5 can be made cationic, by replacing the protective colloid casein in the re-inforcing resin emulsion with 400 cps. methyl cellulose and replacing the anionic emulsifying agent with either of the following: Lauryl pyridinium chloride, cetyl-dimethyl-benzyl ammonium chloride (Triton K-GO), methyl dodecyl benzyl trimethyl ammonium chloride (Hyamine 2389), amongst others.

VAT DYESTUFF PRINTING WITH EXTENDER PRINT PASTES With a number of vat dyestuffs and Various types of extender print pastes, prints were prepared and properly developed. Details of the examples are given here below.

Vat Printing Violet 6R Eight fluid ounces of Vat Printing Violet 6R, were incorporated into a gallon of extender print paste. The mixture was agitated with an Eppenbach Homomixer for a few minutes. The following extender print pastes were tested:

Examples 5, 6 with xylol, 6 with min.' spirits, 8, 9, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 and 36.

In a further set of examples to the Printing Violet 6R 18 parts of Duponol ME dry and 2 parts of Nekal A dry was added for each 100 parts of dry vat pigment. With this special vat pigment paste the following print pastes were made up:

Extender print pastes of Example 5, 6 with xylol, H

22 and 23 one gallon each and 8 fluid ounces of vat pigment paste. Nekal A is a sodium alkyl naphthalene sulfonate.

The above print pastes were printed on a heavy cotton drapery fabric, the prints were dried on hot cans (drums), padded with a solution of '16 potash, 10% Rongalite, 7% glycerine and 68% of water, vat aged for 10 minutes in vat steam ager, oxidized by bichromate method, acetic acid treated and soaped at boil for 5 minutes and dried and ironed. The Rongalite was Rongalite C, sodium formaldehyde sulfoxylate.

A comparative print paste was prepared with the conventional Colloresine process, also called Cellapret process. A print paste was prepared, which contained in a total volume of 136 fluid ounces 8 ounces of Vat Printing Violet 6R. The carrier consisted of parts hot water, 5 parts Glyecine A (a polyglycol derivative humectant), parts of wheat starch paste, 8% strong and 30 parts of 3% solution of 4000 cps. methyl cellulose. Starch, water and humectant is added first, methyl cellulose last. Starch protects the vat pigment. After treatment was similar to the prints above. Padding solution consisted here also of 10% Rongalite, 15% potash, '7% glycerine and 68% water.

In another comparative print 8 ounces of Violet 6R were incorporated into a conventional vat printing paste thickener, using one gallon of same. Prints were Vat aged and soaped, the Soaping following the conventional bichromate and acetic acid `treatments. The print paste contained Rongalite and no padding operation took place here.

The following conclusions could be drawn from the prints: (l) Most all emulsion prints were stronger, than the Colloresine print. (2) The better emulsion prints surpassed in color strength and brilliance the conventional vat comparative print. (3) CMC extender print pastes gave better color development, than MC (methylcellulose) extender printpastes. (4) Mineral spirits yields stronger and more brilliant prints, than xylol. (5) Diluted type extender print pastes improve in color strength, if CMC is used and/or-if Duponol ME solution is added to the print paste, to incorporate in total 0.2 to 0.5% Duponol ME dry on the print paste.

The best color was obtained with print using extender print paste of Example 26 (CMC, min. spirits, low volume type, no re-inforcing resin emulsion); next best with that of Example 25 (CMC, min. spirits, low volume type, plus reinforcing emulsion); next followed closely the extender print pastes of Examples 24 (CMC, min. spir. high volume type, no resin emulsion) and (MC, xylol, no resin emulsion, 0.2% Duponol ME).

Other vat colors The majority of vat dyestuff print pastes prints better and with greater brillance if carboxymethylcellulose is used. Ponsol Golden Orange YL Paste (Du Pont), Ponsol Blue BF Double Paste Du Pont), Indanthrene Blue BFP Double Paste (GDC. Color Index 1113) are examples of vats printing well with CMC extender print pastes. .Ponsol Direct Black 3G Double Paste (Du Pont) is an example of a vat dyestuf, which prints better with methyl cellulose extender print pastes. Other examples of vat dyestuffs suitable for printing with the extender print pastes of this invention are:

Indanthrene Brilliant Pink RN Paste Fine,

AITCC Prototype #109,

Indanthrene Brilliant Violet 4RN Paste Fine,

Color Index 1104,

Sulfanthrene Red 3B Paste, Color Index 1212,

Sulfanthrene Orange R, Paste, Color Index 121'7,

Ponsol Jade Green Double Paste, Color Index Indanthrene Blue CE, Color Index 1112, amongst others.

Printing Rapidogens with extender print pastes The extender pastes of this invention, when used with dyestuffs in general, permit very mild soaping and elimination of cottage steaming, as the prints are soft as printed and no harsh gum has to be Washed out of the print. yFor printing on silk and cellulose acetate rayons mild soaping is of distinct advantage. However, even in cotton printing such an advantage is very handy to the printer.

Extender print paste of the Example #5, was mixed with Rapidogen dyestuff solutions (patented process in making the solutions) using 18% dyestui solution and 82% extender print paste. This corresponds to about 31/2 to 4% dye concentration in the print paste. The following dyestuf solutions were used:

Rapidogen Scarlet RS, solution, AATCC Prototype #170,

Rapidogen Red R solution, AATCC Prototype v#169, and

Rapidogen Blue DN, AATCC Prototype #164.

The prints made with these pastes were very sharp, were soft after drying and were well fixed after conventional acid aging and soaping.` All pastes had nice printing consistency.

Algosol printing with extender print pastes #5, but gave better results with extender of Example #22.

Direct dye printing with extender print pastes Diamine Scarlet BA-CF, Color Index 382, Fastusol Blue Bil-CF, AATCC Prototype #356, and Fastusol Brown LBRA were incorporated into extender print paste of Example in concentration of 3% on total print paste. The pastes became slightly heavier after the dyes were added, printed well and did not require soaping to yield soft hand.

Example 47.-Discharge printing extender print paste.

Discharge printing pastes contain 4 to 18% sodium formaldehyde sulfoxylate in the print paste. It is very difficult to formulate stable oil-in-Water emulsions with such a large proportion of electrolyte. The stability of the extender print pastes of this invention is so great, however, that such a goal can be accomc plished. In this example a solution was prepared as follows: 7 lbs. of a 10% water solution of sodium carboxymethylcellulose, low viscosity type, was first prepared. A sodium formaldehyde sulfoxylate solution was next prepared, by dissolving 8 lbs. of sulfoxylate in 8 lbs. of Water. lThese two solutions were mixed and 2 lbs. of a 10% Duponol ME solution in water was added, totaling 25 lbs. This solution was added slowly under agitation to 50 lbs. of the extender print paste of Example 5 and the resulting product was a discharge printing extender print paste. This paste contained 10.67% sulfoxyiate. The sulfoxylate content of such discharge paste may be varied by changing proportion of solution to emulsion. 4% to 16% sulfoxylate content gives useful limits. This discharge extender print paste can be mixed with oil-in-water resin emulsion color concentrates, as described in my copending application Ser. No. 91,009.

The fabrics are dyed with azo dyes for discharge printing. After printing the fabric is dried and passed through a vat ager. The aged printed fabric is then soaped to remove the decomposition products of the dyes discharged from the fabric and of the sulfoxylate. In an oil-inwater emulsion the sulfoxylate is in the continuous outside phase. Therefore color loss may occur in soaping, as the removal of the decomposition products and excess sulfoxylate may take part of the pigment print with it. To avoid color loss, I have found, that a cationic surface active agent may be used as aftertreatment of the aged prints before anionic soaping is applied. Formaldehyde may be added to the solution of the cationic agent to help to insolubilize the protective colloids. About 1/2% active cationic agent and l to 2% of 40 volume percent formaldehyde is a satisfactory proportion, based on the treating solution. Temperatures of around F. are of advantage. As an alternative: a cationic re-inforcing resin emulsion may be used with a cationic pigment concentrate in the pigment printing.

The discharge printing extender print paste of this example may be used also for vat dyestuif printing. As an illustration of this method, we mix 8 ounces of Printing Violet 6R (iiuid ounces) with one gallon of the emulsion, which contains 16% sulfoxylate. Prints are made in the regular way, can dried, padded and vat aged. The padding solution consists of 15% potash, 7 glycerine and 7 8% water. Other similar padding solutions may be used too. 'I'he padded print may be f dried first, or passed wet into the vat ager. Aging time l0 minutes. The prints are re-oxidized and soaped. This process yields stronger colors (darker and livelier shades) than the conventional Coliorsine process.

Specifications of suitable solvents The above examples show'the use of certain solvents. Here below some specications are given for suitable solvents.

PETROLEUM SOLVENTS Initial boiling points ranging from 210 to 330 F This includes fractions from'V. M. & P. naphtha to high flash point mineral spirits.

This includes Xylol to Specially bleh; llasll. Peint Nephthasand; armati@ hydrocarbons Obtained. from. petroleum.. whoh; usually @Datein some ampliable portion... tiene@ the. lav/.er Igauri-lutanol value.

Lower boiling fractions be also used, like lacquer dluent iraniens. f.. petroleum. alltel-.lts 0rtoluol in the arqroatl.- renee., but.. than rep.- resentlncleased.rehaaarfl- Ievat. pristine the.: usuel. stoner-tiens are. to 1.6. iluld. Quotes of.y vat. oreste@ hasta, @staining to 20% dry dyestuif, and one, gallon extender print pasteemulsion- Asili-@am agentes@ usually in essentielle-1.1.9

to 1%y of. print, paste Surfers. activeaeent @der tion. te mimosas rear ee up. t9. 1% tor Sneeial DurpQSeS.-

Alweet liteit for high Viseositr faellnloseethers can. be. Onsidered t0, be 1.2.00; Gr.5-L ill. 2.1%.- aqueous solutions 1.5.00.- cps, metlofloellulose one.: may @Ome es 19W es 1.200. cpe. in meditation batches...

Most. usiul ranges. for veter.- ere., lll/2 to; ffivb.A and, for weterfimmlscible hydrocarbon solvents 4.3 t0.5.1.1/2%el1.pereeots by. Weight.

PRGPORTQNS 0I.' INGREDENTS, 1N E?? AMPLES. Ir WATER 1s. 1.0.0. PARTS [In examples with reinforcing.; resinemulsions, thev resin 'emulsions were' not consideredand the analysis 1s based ontheresidualpant. 'All partsareby weightJ]- Exanple Numher Solvent. lulose ether.. l. other-'mgdi-ms 5.62 uponol .260 0.536fDuponol.ME. 6' 0.583Dupon01--ME 0. 10422130120110111112.' 9 0.392 DuponollVlE.v

The above tablev .shows thek interrelationship of ingredients 0f the herein described invention.

The dilutedi extender print'V pastesl of Examples Sand 34- are useful only in specific instances, as the comparatively large Water contentreduces intensity and liveliness of prints. nExample 6 the extender print paste was diluted, taking '75 print paste@311.25%vtr-.atary lathe.. efr-'such diluf.. tion it is fV advantage; tbatztlieveeter should hev notI morethan 61%,l the. cellulose ether not more th21M-6%. and the-Solventeontsot-not less than 38%.

In connection with dyestuff printing, it should befmentielleds, thatfse susana woor; acid: colors, ieacid dyes arenonnally andlthisrtype or..

dyestul prints Well with thev print pastesfofvv this invention.

Dyestui printingis advantageously. done. in proportions of 1- to.8.% ofv dyestuff, drybasis, and 92 to. 99% of extender print paste. The water present in the dye dispersion, as marketed, may be considered as diluent. to the. extender print pastes.

Water soluble amine-.aldehyde resins, likey the Aerotex M-3 resin, triazine and urea aldehyde resins (which maybe alkyl and` aryl. substituted and etheried with water soluble alcohols) assist in insolubilizing the cellulose ethers, like methylcellulose. The amine aldehyde resinsmay be used. with advantage in` proportions of' 50% to 250%. of the celluloseether constituent of the pastes. Insolubilization takesv place in dried prints, after curing.. Catalysts may be. present. Whereas. formaldehyde is; the most important aldehydev component of vsuch. resins, acetaldehyde and other higher molecular aldehydes mayf form suitable resins` for this purpose.

I- claim:-

l. An oil-in-.water emulsion textile printing paste useful, as extender for pigment printing and as a carrier for. dyestuff printingy comprising @l1/27ste 56% Water, 0.3,%.to.0.8,% highvisoosty water soluble cellulose ether yielding. inay 2% aqueous solutionl at least 1,200A cps.. viscosity` at 20 C., and 43% to 51l/2% water imnliscible. hydroearbon solvent, all, percents being by` weight, said water-soluble cellulose ether being dissolved in the, Water.

2. The product of claim 1, in which the cellulosey ether is methyl; cellulose,` yieldingA in a 2% aqueous solution at least 1200 cps; viscosity; at 20 C.

3. The product of-claim 11, iirwhichthe cellulose ether Sodium Qerbxymethvlcellulose, yieldingvv in a 2% aqueous solution at least 1200 ops. Viscosity, at 20"-(5.l

4a The product of'claim 1, in which the solvent is an aliphatic-hydrocarbon- 5; The product orfclaim- 1, in whichthesolventv is-an aromatichydrocarbon.

6. The produetvof claini lhinwhich the solvent is a Mineral Spirits fir-action of pet-roleun1`so 1 Vents.

7; Theproduct offclaixn 1-, inwhich the solvent;

of water immiscible hydrocarbon solvent;I and 0.7 to; L6. Rar-ts.. Qt; hshvisoositv waterrsolubleoellurlose ether yielding in a 2% aqueous solutiom at least 1200 cps. viscosity at 20 C., all parts'and percentages being.A bye weight;l saidy water-soluble celluloselether beingdissolved in thewater;

lla The .product of` claimll-l, invlhich` the cellu-A lose. ether.v isineth-y-l cellulose, yieldingfin` aA 2% aqueous: solution at: least 3000' cps.- viseosityatY 20?' Q: andthe solvent is. an. aliphatie petroleum solvent. fraction;` with initial.' boilingpoints:

ranging fromi210to 3300.55'.,` flash points ranging 135 F., K'auri-Butanol values ranging from 75 to 98 1/2and pounds per gallon bulking values ranging from 6.91 to 7 .23 at 60 A 1 13. The process of decorating textile fabrics in a discontinuous 'patternl by' printing said fabrics with a print paste consisting o the product of claim 1 and the coloring medium.

14. The product of claim 1, comprising a water soluble amine-aldehyde resin, said resin being present in quantities ranging from 50% to 250% of the cellulose ether content of the product.

15. A product comprising between 96.5% and 99.75% of an oil-in-water emulsion textile printing paste, said paste comprising water, a high viscosity water soluble cellulose ether and a Water immiscible hydrocarbon solvent, said paste containing`471/2% to 56% water based on the total weight of said paste and also containing for each 100 parts of water, S0 to 110 parts of the water immiscible hydrocarbon solvent and 0.7 to 1.6 parts of the high viscosity water soluble cellulose ether yielding in a 2% aqueous solution at least 1200 cps. viscosity at 20 C., said Water soluble cellulose ether being dissolved in water, said product also comprising between 0.25% and 3.5% of a reinforcing oil-in-water resin emulsion, said proportions being by weight and said percentages of 96.5%, 99.75%, 0.25%, and. 3.5% being based upon the total weight of said product, said 471/2 and 56% percentages being based on the total weight of said printing paste.

16. A print paste containing a vat dyestuii as pigment, comprising (A) one gallon of oil-inwater emulsion textile printing paste, said paste comprising between 47.5% to 56% water, 0.3% to 0.8% high viscosity Water soluble cellulose ether yielding in a 2% aqueous solution at least 1200 cps. viscosity at 20 C., and 43% to 51.5% water immiscible hydrocarbon solvent, said Water soluble cellulose ether being dissolved in the water, wherein the cellulose ether is sodiumcarboxymethylcellulose, said per-cents being by Weight and based on the total weight of said one gallon, and (B) 0.5 to 16 fluid ounces of vat dyestuff paste, said dyestuff paste containing to 20% vat dye dry content, said percentages of dry content being by Weight and based on the Weight of the total fluid ounces of dyestuff paste.

17. A print paste comprising (A) l to 8 parts of a water soluble or water dispersible dyestuff in Water dispersion and (B) 92 to 99 parts of a product comprising 47.5% to 56% Water, 0.3% to 0.8% high viscosity Water soluble cellulose ether yielding in a 2% aqueous solution at least 1200 cps. viscosity at 20 C., and 43% to 51.5% Water immiscible hydrocarbon solvent, said water soluble cellulose ether being dissolved in the water, all parts and percents being by Weight, said percents being based on the total Weight of said product (B).

18. A composition of matter comprising 0.1 to 2 parts of a surface active agent and 100 parts of an oil-in-Water emulsion textile printing paste, said paste comprising 47.5% to 56% Water, 0.3% to 0.8% high viscosity water soluble cellulose 'ether yielding in a'2% aqueouslsolution'at least 11200cps. viscosity at 20 C., .and 43%'.to .51.5% lwater immiscible hydrocarbon solvent, said water soluble cellulose ether being Adissolved in` the Water, all parts .and percents being by Weight, `the ytotal'weight of said parts being the totalweight of said composition of matter and said percents being `based on the total weight of lsaid" textile Vprinting paste. v

19. A composition of matter comprising less .than 1 part oi an anti-foaming agentfand 100 parts of an oil-in-Water emulsion textile printing paste, said paste comprising 47.5% to 56% Water, 0.3% to 0.8% high viscosity Watersoluble cellulose ether yielding in a 2% aqueous solution at least 1200 cps. viscosity'fat` 20"` C., and 43%' to 51.5% water immiscible hydrocarbon solvent, said water soluble cellulose ether being dissolved in the water, all parts and percents being by weight, the total weight of said parts being the total weight of said composition of matter and said per-cents being based on the total Weight of said textile printing paste.

20. A composition of matter comprising 0.25 to 3.5 parts of a reinforcing oil-in-water resin emulsion, less than 1 part of an anti-foaming agent, and 95.5 to 99.75 parts by weight of an oil-in-water emulsion textile printing paste, said paste comprising 47.5% to 56% water, 0.3% to 0.8% high viscosity Water soluble cellulose ether yielding in a 2% aqueous solution at least 1200 cps. viscosity at 20 C., and 43% to 51.5% water immiscible hydrocarbon solvent, said water soluble cellulose ether being dissolved in the water, all parts and percents being by weight, the total Weight of said parts being the total weight of said composition of matter and said per-cents being based on the total weight of said textile printing paste.

21. A composition of matter comprising 0.25 to 3.5 parts of a reinforcing oil-in-water resin emulsion, 0.1 to 2 parts of a surface active agent, and 94.5 to 99.65 parts of an oil-in-water emulsion textile printing paste, said paste comprising 47.5% to 56% water, 0.3% to 0.8% high viscosity water soluble cellulose ether yielding in a 2% aqueous solution at least 1200 cps. viscosity at 20 C., and 43% to 51.5% water immiscible hydrocarbon solvent, said water soluble cellulose ether being dissolved in the Water, all parts and percents being by weight, the total weight of said parts being the total weight of said composition of matter and said per-cents being based on the total weight of said textile printing paste.

22. A composition of matter comprising solutions of sodiumformaldehydesulioxylate and sodiumcarboxymethylcellulose in Water and an oilin-water emulsion textile printing paste,said paste comprising 47.5% to 56% Water, 0.3% to 0.8% high viscosity water soluble cellulose ether yielding in a 2% aqueous solution at least 1200 cps. viscosity at 20 C., and 43% to 51.5% water immiscible hydrocarbon solvent, said water soluble cellulose ether being dissolved in the Water, all percents being by weight, the total weight of said parts being the total weight of said composition of matter and said per-cents being based on the total weight 0f said textile printing paste.

23. The print paste comprising 75 %A of a product which comprises 471/2% to 56% Water, 0.3% to 0.8% high viscosity water-soluble cellulose ether, yielding in a 2% aqueous solution at least 1200 cps. viscosity at 20 C., and 43% to S11/2% water immiscible hydrocarbon solvent, all percents being by weight and based on said product,

said water-solubleceulose ethenbeing: dispersed in` the wanen and 25%- watenofr dilutiomsuitable fonscneen printing; said; 75%` and; 25,1%. based on said print paste',v andi said: psi/nt paste. containing notmone than; water and nosmore'thasn (15%` of celiulose: ether amt nat; lessv 3,8%L of solventi, all, per-cents. by weight;

24'.4 Ai composition. of matter comprising; 0125 to 3.5 parts of a reinforcing oil-in-waten'resm'i-.emulfsion, 011 cm2 parts of a surface.` actmezagent, and

`94.5 to,l 95h65; partsrof an, uil-in-wxiteiaV emuision textile printing: paste, said' paste comprising 4=I725%i;o56%,` Watan. 0.3% to O18 high. viscosity watevsolubl'e cellulose: ether: yielding in 2;. 2;%

aqueous solution at least; 12011: GDS; viscosity at i5 3'336'48'4 bon: solvent; and. ,1ess-thanv one. parts eff an; ant-ir wenn Yseid water-semble cellulose ether being: dissqlyed in the; wate1;; ail pants and, pelcents. being by weight, the mm1 Weigh-ti, of s aid par-ts lmeirigftlieA total weights, of. said; composition ofmatten aand; said; per-cents; being based on. the ttfl'., weghnof: saildftextile. pxinting Paste.

IaASZLO, AUER:.

References; Cited inl vthe 111e-v of this,` patent STATESPAfI'ENTS Name Date Reichel-, M June 1,0,y 1941 Klinkensten Dec,A 141943 Number` 

1. AN OIL-IN-WATER EMULSION TEXTILE PRINTING PASTE USEFUL AS EXTENDER FOR PIGMENT PRINTING AND AS A CARRIER FOR DYESTUFF PRINTING COMPRISING 47 1/2% TO 56% WATER, 0.3% TO 0.8% HIGH VISCOSITY WATER SOLUBLE CELLULOSE ETHER YIELDING IN A 2% AQUEOUS SOLUTION AT LEAST 1200 CPS. VISCOSITY AT 20* C., AND 43% TO 51 1/2% WATER IMMISCIBLE HYDROCARBON SOLVENT, ALL PERCENTS BEING BY WEIGHT, SAID WATER-SOLUBLE CELLULOSE ETHER BEING DISSOLVED IN THE WATER.
 14. THE PRODUCT OF CLAIM 1, COMPRISING A WATER SOLUBLE AMINE-ALDEHYDE RESIN, SAID RESIN BEING PRESENT IN QUANTITIES RANGING FROM 50% TO 250% OF THE CELLULOSE ETHER CONTENT OF THE PRODUCT. 